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Shell Higher Olefins Process

Conversion of Ethylene to Higher Olefins Using Homogeneous Catalysis


By Timothy Barnhill, Joshua Blease, Hassan Abuthaibah, Nick Nadorff

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Higher Olefins in Industry


Olefins (ethylene, butylene)
Key building blocks High availability, reactivity, low cost

Higher molecular weight olefins (C6-C20)


Synthetic automotive oils Biodegradable surfactants Stronger plastics

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Production of Higher Olefins


Wax Pyrolyis (Chevron, 1966)
Conversion of 20-40% per pass Higher conversions produced undesired aromatics

Ethylene Oligomerization (Gulf Oil, 1966)


Production of wide variety of alkenes Modifying selectivity for desired olefins was difficult

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Shell Higher Olefin Process (1977)


Able to adjust product output to meet market needs Produced -olefins which could be sold as is Converted olefins with low market value to detergent range fatty alcohols (C6-C11)

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Process Overview

B. Reuben
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Process Overview
Oligomerization:

Isomerization:

Metathesis:

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Oligomerization
Oligomer Complex consisting of a few monomers Catalyst Nickel complex Ethylene oligomerized into even -olefins
Desired olefins recovered by distillation Non-marketable olefins sent to isomerization
(usually small (< C6) and large (> C18) olefins)

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Even-numbered -olefins Ni Catalyst

Ligands added

Coordination Complex

Oligomerization Mechanism
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Ethylene reacts

Isomerization
Smaller and larger -olefins isomerized to form internal double bonds Catalyst Na/K on Al2O3

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Metathesis
Metathesis is defined as a catalytic reaction in which alkenes are converted into products by breaking and reforming C-C double bonds.

Phillips Petroleum developed a unique reaction called olefin metathesis. Originally developed to convert cheap propylene into high value ethylene and 2-butene.
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Internal Olefins
The internal olefins pass to the metathesis reactor where the short- and long-chain internal olefins disproportionate.

After this the products of the metathesis reaction are fed to the fractionating column to separate desired C10-14 olefins for hydroformulation.
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Applications of Linear Olefins


Drilling Fluid: (C16 C18) alpha olefins
Physical properties
High purity Viscosity

Monomers: (C4 C10) alpha olefins


Production of polymers and polyethylene

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Detergents: (C12 C20) alpha olefins

Plasticizers: (C6 C10) alpha olefins


Production of plasticizer alcohols and surfactants.

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References
Shell Higher Olefins Process, E.F. Lutz, Shell Development Company, Journal of Chemical Education, 63 (3) p. 202, 1986. The SHOP process: An example of industrial creativity, Bryan Reuben and Harold Wittcoff, Journal of Chemical Education, 65 (7) p. 605, 1988. Developments in LAO Comonomer Technologies for Polyethylene, Nexant, Inc., http://www.chemsystems.com/about/cs/news/items/PERP2011 S11_LAOr.cfm
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